CA2194098A1 - Method of producing 1,2-butylene oxide - Google Patents
Method of producing 1,2-butylene oxideInfo
- Publication number
- CA2194098A1 CA2194098A1 CA002194098A CA2194098A CA2194098A1 CA 2194098 A1 CA2194098 A1 CA 2194098A1 CA 002194098 A CA002194098 A CA 002194098A CA 2194098 A CA2194098 A CA 2194098A CA 2194098 A1 CA2194098 A1 CA 2194098A1
- Authority
- CA
- Canada
- Prior art keywords
- palladium
- butylene oxide
- rhenium
- catalyst
- hydrogenation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 238000000034 method Methods 0.000 title claims abstract description 20
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 title claims abstract description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 23
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 13
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 13
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims abstract description 13
- GXBYFVGCMPJVJX-UHFFFAOYSA-N Epoxybutene Chemical compound C=CC1CO1 GXBYFVGCMPJVJX-UHFFFAOYSA-N 0.000 claims abstract description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 4
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 3
- 238000002360 preparation method Methods 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 5
- 238000005984 hydrogenation reaction Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000000010 aprotic solvent Substances 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 235000010650 Hyssopus officinalis Nutrition 0.000 description 1
- 240000001812 Hyssopus officinalis Species 0.000 description 1
- WPPOGHDFAVQKLN-UHFFFAOYSA-N N-Octyl-2-pyrrolidone Chemical compound CCCCCCCCN1CCCC1=O WPPOGHDFAVQKLN-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019571 Re2O7 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- -1 for example Inorganic materials 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229940099990 ogen Drugs 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003281 rhenium Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6567—Rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Epoxy Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Cosmetics (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Debugging And Monitoring (AREA)
- Devices For Executing Special Programs (AREA)
- Stored Programmes (AREA)
Abstract
The invention concerns a method of producing 1,2-butylene oxide by the catalytic hydrogenation of vinyl oxirane, the method calling for the use of a palladium catalyst on a barium sulphate, zirconium oxide or titanium dioxide support or the use of a rhenium-containing palladium catalyst on a support.
Description
BASFAI~"-.. ' I':CHAFT 2 1 9 4 0 9 8 o.z.ooso/44981 Preparation Of 1 ,2-Butylene Oxide The plesenl invention relates to a process for the preparation of 1,2-butylene oxide by the catalytic hyd~ ogerlation of vinyl oxirane The catalytic hydrogenation of vinyl oxirane over catalysts consisling of palladium s on aluminum oxide or palladium on activated charcoal is described in US-A
5,077,418 and US-A 5,117,013 and also in Neftekllimiya 33,131 (1993). The yields, selectivities and conver~ions in this process are u"salisractory.
It was the object of the presenl invention to provide a process for the preparation .0 of 1,2-butylene oxide, which makes it possible to prepare 1 ,2-butylene oxide from vinyloxirane with better conversions, yields, and selectivities than in the prior art.
Accordingly, we have found a process for the preparation of 1 ,2-butylene oxide by the catalytic hyd~os~e"ation of vinyl oxirane, wherein use is made of a palladium catalyst on a support of barium sulfate, zirconium dioxide or titanium dioxide or a rhenium-containing suppo, led palladium catalyst.
When carrying out the process of the invention, the vinyl oxirane or solutions of vinyl oxirane are h~d~ugellated in a solvent which is inert under the reaction 20 conditions in the presence of the catalysts to be used in the invention at temperatures generally of from -10~ to 1 OO~C, preferably from -5~ to 50~C and more pleferably from 0~ to 30~C under a pressure of from 1 to 100 bar, pre~erably from 1 to 50 bar, in particular from 1 to 30 bar.
25 The process of the invention can be carried out without the use of solvents or, advantageously, in the presence of a solvent inert under the reaction conditions, for example, in the presence of alcohols, such as methanol, ethanol, propanol, isop,opanol, n-butanol, isobutanol or tert-butanol, hydrocarbons, such as petrol-eum ether, benzene, toluene or xylene, or dipolar-aprotic solvents, such as N-30 alkyllactams, eg N-methylp~ olidone or N-octylpyrrolidone, or, in particular,ethers, such as tetrahydrofuran, dioxane, methyl-tert-butyl ether, di-butyl ether, dimethoxy ethane, diethyl ether or diiso~Jropyl ether.
The process of the invention can be carried out either continuously or batchwise, 35 in the gas phase or in the liquid phase. When the process is carried out continuously, tubular reactors or cascades of reactors can be used for example, which can be operated in the upward-flow mode or downward-flow mode.
5,077,418 and US-A 5,117,013 and also in Neftekllimiya 33,131 (1993). The yields, selectivities and conver~ions in this process are u"salisractory.
It was the object of the presenl invention to provide a process for the preparation .0 of 1,2-butylene oxide, which makes it possible to prepare 1 ,2-butylene oxide from vinyloxirane with better conversions, yields, and selectivities than in the prior art.
Accordingly, we have found a process for the preparation of 1 ,2-butylene oxide by the catalytic hyd~os~e"ation of vinyl oxirane, wherein use is made of a palladium catalyst on a support of barium sulfate, zirconium dioxide or titanium dioxide or a rhenium-containing suppo, led palladium catalyst.
When carrying out the process of the invention, the vinyl oxirane or solutions of vinyl oxirane are h~d~ugellated in a solvent which is inert under the reaction 20 conditions in the presence of the catalysts to be used in the invention at temperatures generally of from -10~ to 1 OO~C, preferably from -5~ to 50~C and more pleferably from 0~ to 30~C under a pressure of from 1 to 100 bar, pre~erably from 1 to 50 bar, in particular from 1 to 30 bar.
25 The process of the invention can be carried out without the use of solvents or, advantageously, in the presence of a solvent inert under the reaction conditions, for example, in the presence of alcohols, such as methanol, ethanol, propanol, isop,opanol, n-butanol, isobutanol or tert-butanol, hydrocarbons, such as petrol-eum ether, benzene, toluene or xylene, or dipolar-aprotic solvents, such as N-30 alkyllactams, eg N-methylp~ olidone or N-octylpyrrolidone, or, in particular,ethers, such as tetrahydrofuran, dioxane, methyl-tert-butyl ether, di-butyl ether, dimethoxy ethane, diethyl ether or diiso~Jropyl ether.
The process of the invention can be carried out either continuously or batchwise, 35 in the gas phase or in the liquid phase. When the process is carried out continuously, tubular reactors or cascades of reactors can be used for example, which can be operated in the upward-flow mode or downward-flow mode.
2 1 ~4~98 BASFA~ C~HAFT o.z.ooso/44981 ' Advantageously, the catalysts are arranged in these reactors in the form of a fixed bed. When the process is carried out batchwise, the catalyst can be used, eg, instirred reactors in the form of a susper,sion or, advantageously, as a fixed bed, eg, when use is made of recycle reactors.
s The palladium content of the catalysts which can be used in the invention is generally from 0.1 to 5 wt%, preferably from 0.3 to 3 wt~ and more preferably from 0.5 to 2 wt~b, calculated as Pd and based on the total weight of the catalyst.
I
The rhenium-containing supported palladium catalysts which can be used in the invention contain rhenium in a ratio, by weight, in relation to palladium, generally of 1 to 99"~)re~er~dbly 10 to 90, and more preferably 40 to 60.
Apart from the support materials which can be advantageously used for the catalysts containing only palladium as active ingredient ie barium sulfate, zirconium dioxide, or titanium dioxide, other support materials, such as activated charcoal, silicon dioxide, silica gel, or kieselguhr can also be used to advantage.
The preparation of the palladium catalysts or the catalysts containing palladiumzO and rhenium can be effected in conventional manner, for example, by impregnating the support materials with aqueous solutions of water-soluble compounds of p~ dium or of palladium and rhenium, for example, with the nitrates, sulfates, halides, or carboxylates of palladium and rhenium, drying the impregnated supports, eg, at temperatures of from 50~ to 200~C, preferably from 100~ to 25 150~C, then effecting calcination at temperatures generally of from 200~ to 600~C, preferably at a temperature of from 300~ to 500~C, and reducing the catalyst thus obtained by treatment with reducing agents, such as hydrazine, hydrogen, or hydrogenous gases, for example, at temperat.lres of from 100~ to 300~C, p,ererably at a temperature of from 150~ to 250~C. When carrying out 30 reduction and activation of the catalyst with hyd~ogen, reduction is generally continued until no more appreciable amounts of water are formed.
The reduction and activation of the catalysts with hydlogel) can take place in situ in the hyd~ogel,ali"g reactor during hydlogenalion, but the catalysts are preferably 35 reduced and activated prior to their use in the process of the invention.
When use is made of thermally unstable salts of palladium and rhenium for i,npreyllation of the support material the activation of the catalyst can alternatively take place thermally by heating the impregnated supports to temperatures generally of from 100~ to 700~C, and preferably of from 200~ to 600~C.
BASFAKTIENGEsELLscHAFT o.z.ooso/44981 Instead of using the aforementioned palladium or rhenium salts, water-soluble palladium complex compounds or water-soluble salts of the oxyacids of rhenium, for example, alkali metal or ammonium rhenates or per,l,enal~s and solutions of rhenium heptoxide ~Re2O7) can be used for impregnation of the supports.
s When preparing palladium and rhenium-containing supported catalysts, the elements rhenium and palladium can be applied to the support material simultaneously or successively for impreyllation of the support material.
The purification of the reaction mixture in order to isolate 1,2-butylene oxide can take place in conventional manner, eg, by distillation.
The vinyl oxirane required as starting material can be prepared, eg, by the method described in US-A 4,897,498 by partial oxidation of 1,3-butadiene over silver catalysts.
1 ,2-butylene oxide can be used, eg, as fuel additive or as stabilizer for chlorinated hydrocarbons.
zo Examples Hydrogenation of vinyl oxirane to 1,2-butylene oxide was carried out in a stirred autoclave having a capacity of 50 mL. In each case, the reactor was charged with0.1 g of the respective catalyst and 2.5g of vinyl oxirane in 22.5g of 25 tetrahydrofuran.
The hydrogenating co"diliGns temperature, pressure, and reside"ce time and the degree of hyd~uge,lation obtained (determined by calibrated gas chromatography of the hyd~ogenated effluent) are listed in the table.
2t 94098 SFA~ . I c~HP.FT o.z.ooso/44981 Table Catalyst* Hyd~u~l,dliul, Pressure Re~?~"ce Conversion Yield [~7]
Te""~ldlure T~me [~C] [bar] [h] [~] 1,2-B BA n-BuOH
0.5 ~o Pd/BaSO4 20 20 9 100 6714 1 1 ~o Pd/BaS04 0 4 15 100 82 4 6 ~o Pd/BaS04 0 20 12 100 81 5 2 1.5~O Pd/BaS04 20 4 15 100 7017 10 ~o Pd/ZrO2 20 8 15 100 6020 14 3 ~o Pd+35~Re/C 0 20 11 100 75 6 9 0.5~o Pd+0.5~oRe/A1203 50 40 8 100 71 9 8 *Percentages by weight, based on total catalyst 1 ,2-B: 1 ,2-butylene oxide BA: n-butyraldehyde n-BuOH: n-butanol
s The palladium content of the catalysts which can be used in the invention is generally from 0.1 to 5 wt%, preferably from 0.3 to 3 wt~ and more preferably from 0.5 to 2 wt~b, calculated as Pd and based on the total weight of the catalyst.
I
The rhenium-containing supported palladium catalysts which can be used in the invention contain rhenium in a ratio, by weight, in relation to palladium, generally of 1 to 99"~)re~er~dbly 10 to 90, and more preferably 40 to 60.
Apart from the support materials which can be advantageously used for the catalysts containing only palladium as active ingredient ie barium sulfate, zirconium dioxide, or titanium dioxide, other support materials, such as activated charcoal, silicon dioxide, silica gel, or kieselguhr can also be used to advantage.
The preparation of the palladium catalysts or the catalysts containing palladiumzO and rhenium can be effected in conventional manner, for example, by impregnating the support materials with aqueous solutions of water-soluble compounds of p~ dium or of palladium and rhenium, for example, with the nitrates, sulfates, halides, or carboxylates of palladium and rhenium, drying the impregnated supports, eg, at temperatures of from 50~ to 200~C, preferably from 100~ to 25 150~C, then effecting calcination at temperatures generally of from 200~ to 600~C, preferably at a temperature of from 300~ to 500~C, and reducing the catalyst thus obtained by treatment with reducing agents, such as hydrazine, hydrogen, or hydrogenous gases, for example, at temperat.lres of from 100~ to 300~C, p,ererably at a temperature of from 150~ to 250~C. When carrying out 30 reduction and activation of the catalyst with hyd~ogen, reduction is generally continued until no more appreciable amounts of water are formed.
The reduction and activation of the catalysts with hydlogel) can take place in situ in the hyd~ogel,ali"g reactor during hydlogenalion, but the catalysts are preferably 35 reduced and activated prior to their use in the process of the invention.
When use is made of thermally unstable salts of palladium and rhenium for i,npreyllation of the support material the activation of the catalyst can alternatively take place thermally by heating the impregnated supports to temperatures generally of from 100~ to 700~C, and preferably of from 200~ to 600~C.
BASFAKTIENGEsELLscHAFT o.z.ooso/44981 Instead of using the aforementioned palladium or rhenium salts, water-soluble palladium complex compounds or water-soluble salts of the oxyacids of rhenium, for example, alkali metal or ammonium rhenates or per,l,enal~s and solutions of rhenium heptoxide ~Re2O7) can be used for impregnation of the supports.
s When preparing palladium and rhenium-containing supported catalysts, the elements rhenium and palladium can be applied to the support material simultaneously or successively for impreyllation of the support material.
The purification of the reaction mixture in order to isolate 1,2-butylene oxide can take place in conventional manner, eg, by distillation.
The vinyl oxirane required as starting material can be prepared, eg, by the method described in US-A 4,897,498 by partial oxidation of 1,3-butadiene over silver catalysts.
1 ,2-butylene oxide can be used, eg, as fuel additive or as stabilizer for chlorinated hydrocarbons.
zo Examples Hydrogenation of vinyl oxirane to 1,2-butylene oxide was carried out in a stirred autoclave having a capacity of 50 mL. In each case, the reactor was charged with0.1 g of the respective catalyst and 2.5g of vinyl oxirane in 22.5g of 25 tetrahydrofuran.
The hydrogenating co"diliGns temperature, pressure, and reside"ce time and the degree of hyd~uge,lation obtained (determined by calibrated gas chromatography of the hyd~ogenated effluent) are listed in the table.
2t 94098 SFA~ . I c~HP.FT o.z.ooso/44981 Table Catalyst* Hyd~u~l,dliul, Pressure Re~?~"ce Conversion Yield [~7]
Te""~ldlure T~me [~C] [bar] [h] [~] 1,2-B BA n-BuOH
0.5 ~o Pd/BaSO4 20 20 9 100 6714 1 1 ~o Pd/BaS04 0 4 15 100 82 4 6 ~o Pd/BaS04 0 20 12 100 81 5 2 1.5~O Pd/BaS04 20 4 15 100 7017 10 ~o Pd/ZrO2 20 8 15 100 6020 14 3 ~o Pd+35~Re/C 0 20 11 100 75 6 9 0.5~o Pd+0.5~oRe/A1203 50 40 8 100 71 9 8 *Percentages by weight, based on total catalyst 1 ,2-B: 1 ,2-butylene oxide BA: n-butyraldehyde n-BuOH: n-butanol
Claims (6)
1. A process for the preparation of 1,2-butylene oxide by the catalytic hydrogenation of vinyl oxirane, wherein a palladium catalyst on a support of barium sulfate, zirconium dioxide or titanium dioxide or a rhenium-containing supportedpalladium catalyst is used.
2. A process as defined in claim 1, wherein use is made of a palladium catalyst having a palladium content of from 0.1 to 5 wt%.
3. A process as defined in claim 1 and claim 2, wherein use is made of a palladium catalyst having a palladium content of from 0.3 to 3 wt%.
4. A process as defined in any of claims 1 to 3, wherein the hydrogenation is carried out at a temperature of from -10° to 100°C and under a pressure of from 1 to 100 bar.
5. A process as defined in any of claims 1 to 4, wherein the hydrogenation is carried out in a solvent.
6. A process as defined in any of claims 1 to 5, wherein the hydrogenation is carried out in a dipolar-aprotic solvent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4422046A DE4422046A1 (en) | 1994-06-27 | 1994-06-27 | Process for the preparation of 1,2-butylene oxide |
| DEP4422046.4 | 1994-06-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2194098A1 true CA2194098A1 (en) | 1996-01-04 |
Family
ID=6521357
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002194098A Abandoned CA2194098A1 (en) | 1994-06-27 | 1995-06-16 | Method of producing 1,2-butylene oxide |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US5770747A (en) |
| EP (1) | EP0767785B1 (en) |
| JP (1) | JPH10502063A (en) |
| CN (1) | CN1075065C (en) |
| AT (1) | ATE172728T1 (en) |
| AU (1) | AU2883895A (en) |
| CA (1) | CA2194098A1 (en) |
| DE (2) | DE4422046A1 (en) |
| ES (1) | ES2122645T3 (en) |
| MX (1) | MX9700117A (en) |
| WO (1) | WO1996000222A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19602710A1 (en) * | 1996-01-26 | 1997-07-31 | Basf Ag | Process for the selective hydrogenation of vinyloxirane to 1,2-butylene oxide over heterogeneous catalysts |
| DE19616736A1 (en) * | 1996-04-26 | 1997-11-06 | Basf Ag | Selective aromatization catalyst |
| EP1551032A4 (en) * | 2002-10-11 | 2008-03-26 | Yoshiaki Arata | Hydrogen condensate and method of generating heat therewith |
| US10300155B2 (en) | 2015-12-31 | 2019-05-28 | Washington University | Alpha-synuclein ligands |
| CN109068741A (en) | 2016-04-20 | 2018-12-21 | 菲利普莫里斯生产公司 | Hybrid aerosol-generating element and method for manufacturing a hybrid aerosol-generating element |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3005832A (en) * | 1961-10-24 | Epoxy alcohol production | ||
| US2561984A (en) * | 1949-04-25 | 1951-07-24 | Phillips Petroleum Co | Production of primary alcohols and aldehydes |
| US3336241A (en) * | 1963-11-12 | 1967-08-15 | Shell Oil Co | Process for preparing epoxy compounds and resulting products |
| US4127594A (en) * | 1978-02-21 | 1978-11-28 | Shell Oil Company | Selective hydrogenation of olefinic impurities in epichlorohydrin |
| US4897498A (en) * | 1988-01-28 | 1990-01-30 | Eastman Kodak Company | Selective monoepoxidation of olefins |
| US5117013A (en) * | 1990-05-03 | 1992-05-26 | Eastman Kodak Company | Process for the selective hydrogenation γ, δ-epoxyalkenes to epoxyalkanes |
| US5077418A (en) * | 1990-05-03 | 1991-12-31 | Eastman Kodak Company | Process for the selective hydrogenation γ,δ-epoxyalkenes to epoxyalkanes |
| US5391773A (en) * | 1994-06-17 | 1995-02-21 | Eastman Chemical Company | Process for the selective hydrogenation of epoxyalkenes to epoxyalkanes |
-
1994
- 1994-06-27 DE DE4422046A patent/DE4422046A1/en not_active Withdrawn
-
1995
- 1995-06-16 DE DE59504086T patent/DE59504086D1/en not_active Expired - Fee Related
- 1995-06-16 CN CN95193853A patent/CN1075065C/en not_active Expired - Fee Related
- 1995-06-16 ES ES95924255T patent/ES2122645T3/en not_active Expired - Lifetime
- 1995-06-16 AT AT95924255T patent/ATE172728T1/en not_active IP Right Cessation
- 1995-06-16 EP EP95924255A patent/EP0767785B1/en not_active Expired - Lifetime
- 1995-06-16 US US08/765,618 patent/US5770747A/en not_active Expired - Fee Related
- 1995-06-16 JP JP8502762A patent/JPH10502063A/en active Pending
- 1995-06-16 AU AU28838/95A patent/AU2883895A/en not_active Abandoned
- 1995-06-16 MX MX9700117A patent/MX9700117A/en not_active Application Discontinuation
- 1995-06-16 CA CA002194098A patent/CA2194098A1/en not_active Abandoned
- 1995-06-16 WO PCT/EP1995/002337 patent/WO1996000222A1/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| EP0767785A1 (en) | 1997-04-16 |
| CN1075065C (en) | 2001-11-21 |
| AU2883895A (en) | 1996-01-19 |
| WO1996000222A1 (en) | 1996-01-04 |
| ES2122645T3 (en) | 1998-12-16 |
| JPH10502063A (en) | 1998-02-24 |
| EP0767785B1 (en) | 1998-10-28 |
| DE59504086D1 (en) | 1998-12-03 |
| MX9700117A (en) | 1997-06-28 |
| ATE172728T1 (en) | 1998-11-15 |
| US5770747A (en) | 1998-06-23 |
| CN1151739A (en) | 1997-06-11 |
| DE4422046A1 (en) | 1996-01-04 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |